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Influence of roasting conditions on the biogenic amine content in cocoa beans of different Theobroma cacao cultivars

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Abstract

The objective of this study was to investigate how roasting process conditions affected the content of biogenic amines in cocoa beans of different Theobroma cacao varieties. The raw cocoa beans were roasted at four different temperatures (ranging from 110 °C to 150 °C) and three different air humidities (0.3% to 5.0%). Roasting process may significantly modify the profile and levels of biogenic amines. Tyramine was the most abundant amine in raw cocoa beans, followed by tryptamine and 2-phenylethylamine. Serotonin and dopamine were presented only in small amounts. However, it was found that roasted cocoa beans contained mainly 2-phenylethylamine, followed by tyramine, tryptamine, serotonin and dopamine. Parameters of roasting have a significant effect on the levels of each amine in all types of roasted beans. The highest amount of biogenic amines was observed in the samples roasted at the highest temperatures and in the air with increased humidity. In addition, the results revealed that the cacao cultivars significantly affect the levels of biogenic amines.

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... These compounds will also be impacted in other stages of the process, especially roasting. These new modifications that occur in the most diverse processing steps, all will affect the formation and degradation of bioactive amines [9,11,34]. ...
... It is interesting to observe that the increase in phenylethylamine was most evident in PS 1319, suggesting that this variety is richer in free phenylalanine compared to Parazinho. The enhanced levels of phenylethylamine in the roasted cocoa are important, as this amine is associated with mood modulation, and has beneficial effects on human health [34,37]. ...
... Delgado-Orpina and colleagues [25] found changes after roasting, including a greater content of some bioactive amines. Studies indicate that Strecker degradation forms these amines during the thermal decarboxylation of amino acids in the presence of α-dicarbonyl compounds formed during the Maillard reaction or lipid peroxidation [34,38,39]. ...
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During cocoa processing, there can be the formation of bioactive amines, which are compounds that play relevant roles not only in plant development but also in human health. Thus, we aimed to investigate the presence and levels of bioactive amines during the processing of two important varieties of cocoa (PS 1319 and Parazinho). The seeds were fermented using five different pulp proportions: 100% (E1), 80% (E2), 60% (E3), and 0% (total pulp removal) (E4). The beans were fermented and dried on a farm following traditional procedures. Soon after, they were roasted and processed into chocolates with 60% cocoa in the laboratory. Bioactive amine contents were determined by ion-pair reversed-phase HPLC and fluorometric detection in the samples before, during, and after fermentation, after drying and roasting (nibs), and in the liquor and chocolate. The only amines found before processing in PS 1319 and Parazinho, respectively, in dry weight basis (dwb), were putrescine (pulp, 13.77 and 12.31; seed, 5.88 and 4.58) and serotonin (seed, 2.70 and 2.54). Fermentation was shorter for Parazinho (156 h) compared to PS 1319 (180 h). The changes in amines were affected by the cocoa variety. During drying, the presence of cadaverine stood out, appearing in all treatments of the PS 1319 variety, reaching 17.96 mg/kg dwb, and in two treatments of the Parazinho variety (100 and 60% pulp). During roasting, most of the amines decreased, except for phenylethylamine, which increased up to 2.47 mg/kg dwb for Parazinho and 1.73 mg/kg dwb for PS 1319. Most of the amines formed and built up (e.g., tyramine, putrescine, and cadaverine) during fermentation were not available or were at low levels in the nibs. Most of the amines found during processing did not reach the final product (chocolate), except for cadaverine in PS 1319 without pulp (7.54 mg/kg dwb). Finally, we confirmed how pulp content, processing, and variety influence the content of bioactive amines in cocoa and chocolate. These changes can be better demonstrated through a heatmap and principal component analysis.
... A decrease of bioactive compounds, such as BAs and polyphenolic compounds, occurs in different steps of the cocoa beans processing, affecting their final content and functional properties in cocoa derivatives [10][11][12]. During roasting, physical and chemical changes occur in the beans, such as differences in colour, removal of undesirable volatile compounds, formation of desirable aroma and flavour, reduction of water content (up to 2%), and formation of a brittle structure, as well as changes in flavanols, proanthocyanidins and antioxidant activity [13,14]. ...
... In addition, peculiar cocoa volatile compounds are generated by Maillard reactions and their release is favoured by modifications of the matrix structure [15]. In spite of this, during roasting critical changes may also take place such as the formation of water-insoluble melanoidins, the degradation of catechin-containing compounds [16], the reduction of polyphenol content and antioxidant activity [17], and an increase of the biogenic amines content [12]. If some Maillard Reaction products, such as melanoidins, are required for the development of the peculiar cocoa sensory characteristics and brown colour, some furanic compounds are supposed to have negative effects on human health, as they can show cytotoxicity at high concentration and are "possibly carcinogenic to humans" [18]. ...
... To the best of our knowledge, there are no studies reporting the occurrence of CAD and HIS in raw cocoa beans, although there are few studies where BAs are identified in cocoa. Some authors [12] found tyramine, 2-phenylethylamine, tryptamine, serotonin, and dopamine in different varieties of raw cocoa beans; other authors [11] also found spermidine and spermine in Brazilian samples during fermentation. ...
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The composition of microbiota and the content and pattern of bioactive compounds (biogenic amines, polyphenols, anthocyanins and flavanols), as well as pH, color, antioxidant and reducing properties were investigated in fermented Criollo cocoa beans and shells. The analyses were conducted after fermentation and drying (T1) and after two thermal roasting processes (T2, 120 °C for 22 min; T3, 135 °C for 15 min). The fermentation and drying practices affected the microbiota of beans and shells, explaining the great variability of biogenic amines (BAs) content. Enterobacteriaceae were counted in a few samples with average values of 103 colony forming units per gram (CFU g−1), mainly in the shell, while Lactobacillus spp. was observed in almost all the samples, with the highest count in the shell with average values of 104 CFU g−1. After T1, the total BAs content was found to be in a range of 4.9÷127.1 mg kg−1DFW; what was remarkable was the presence of cadaverine and histamine, which have not been reported previously in fermented cocoa beans. The total BAs content increased 60% after thermal treatment T2, and of 21% after processing at T3, with a strong correlation (p < 0.05) for histamine (ß = 0.75) and weakly correlated for spermidine (ß = 0.58), spermine (ß = 0.50), cadaverine (ß = 0.47) and serotonine (ß = 0.40). The roasting treatment of T3 caused serotonin degradation (average decrease of 93%) with respect to unroasted samples. However, BAs were detected in a non-alarming concentration (e.g., histamine: n.d ÷ 59.8 mg kg−1DFW; tyramine: n.d. ÷ 26.5 mg kg−1DFW). Change in BAs level was evaluated by principal component analysis. PC1 and PC2 explained 84.9% and 4.5% of data variance, respectively. Antioxidant and reducing properties, polyphenol content and BAs negatively influenced PC1 with both polyphenols and BA increasing during roasting, whereas PC1 was positively influenced by anthocyanins, catechin and epicatechin.
... Nacional ("National") is a worldwide recognized cocoa variety produced in Ecuador and classified as "fine" grade, together with Criollo and Trinitario cocoas. It differs from other varieties by having a very short fermentation and yielding seeds of an excellent taste and aroma (Afoakwa et al., 2011(Afoakwa et al., , 2008Dand, 2011b;Kongor et al., 2016;Motamayor et al., 2008;Oracz and Nebesny, 2014). Nowadays, there are few materials of pure Nacional cocoa, being the predominant plantations natural hybrids between pure Nacional and Trinitario beans introduced from Venezuela and Trinidad. ...
... The upper limit values for these cocoas was higher than those obtained in this study. This variation between studies could rely on main factors affecting the phenolic content of cocoa beans, both intrinsic factors such as the genotype and extrinsic factors such as the harvest season and postharvest processes (fermentation and drying) (Afoakwa et al., 2011;Oracz and Nebesny, 2014;Wollgast and Anklam, 2000). ...
... It is known that geographical differences widely affect the cocoa beans TPC (Afoakwa et al., 2011;Oracz and Nebesny, 2014;Wollgast and Anklam, 2000). In this study, samples harvested in the Amazonian region cantons showed higher TPC than those obtained for Pacific Coast ones (between 42.75 ± 8.19 and 71.66 ± 3.94 mg GAE/g and between 33.55 ± 5.74 and 47.40 ± 6.20 mg GAE/g, respectively). ...
... It was found that yeasts, filamentous fungi, lactic and acetic acid bacteria as well as members of the genus Bacillus, are typically present, all of them being able to produce BAs [43]. As a consequence of the protection mechanism of bacteria against the acid medium, decarboxylase activity is favored by low pH values during fermentation [44]. Moreover, contaminating bacteria can also decarboxylate amino acids to support a further accumulation of BAs. ...
... On the contrary, considering samples of the same geographical origin, Oracz and Nebesny (2014) reported for raw cocoa beans from Ecuador and Indonesia, much lower total BAs content, not exceeding 5.0 and 6.0 mg kg −1 , respectively. However, only five BAs were considered in this study, neglecting natural polyamines PUT, SPM, and SPD, as well as, HIS and CAD, representing in our study the most abundant compounds [44]. ...
... Guillen-Casla et al. (2012) [20] reported that TYR, PHE, serotonin, and HIS were the main amines in cocoa beans, although also PUT, dopamine, and ethanolamine have also been determined. Comparison among samples of same geographical origin (samples 1 and 7), displayed comparable (Ecuador) or higher (Indonesia) amounts of PHE, while our samples always showed much higher concentration of TYR for both raw cocoa beans [44]. In addition, do Carmo Brito et al. (2017) [5] found different results. ...
Article
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Biogenic amines (BAs), polyphenols, and aroma compounds were determined by chromatographic techniques in cocoa beans of different geographical origin, also considering the effect of roasting (95, 110, and 125 °C). In all samples, methylxantines (2.22–12.3 mg kg−1) were the most abundant followed by procyanidins (0.69–9.39 mg kg−1) and epicatechin (0.16–3.12 mg kg−1), all reduced by heat treatments. Volatile organic compounds and BAs showed variable levels and distributions. Although showing the highest BAs total content (28.8 mg kg−1), Criollo variety presented a good aroma profile, suggesting a possible processing without roasting. Heat treatments influenced the aroma compounds especially for Nicaragua sample, increasing more than two-fold desirable aldehydes and pyrazines formed during the Maillard cascade and the Strecker degradation. As the temperature increased, the concentration of BAs already present in raw samples increased as well, although never reaching hazardous levels.
... Also tea, coffee, and cocoa, as well as their derivatives, have been considered as a source of BAs, although few studies are present in the literature, mainly regarding raw materials ( Cirilo et al., 2003;Casal et al., 2004;Vasconcelos et al., 2007;Palavan-Unsal et al., 2007;Oracz and Nebesny, 2014). Profiles and concentrations are reported to be very much varied as these molecules can be formed/accumulated in relation with the type and quality of raw materials, their origin and processing which in turn is driven by manufacturing technology, agronomic conditions, trading, blend, storage, and distribution of these commodities ( Dias et al., 2012;Zhang et al., 2014;Restuccia et al., 2016;CarmoBrito et al., 2017). ...
... In this way, UHPLC allows excellent separations in shorter analysis time compared to those obtained by conventional LC. However, the direct separation of BAs is difficult in reversed-phase mode so that precolumn derivatization has usually been performed in UHPLC methods (Oracz and Nebesny, 2014). Finally, LC-ELSD methodology showed accurate and precise determination of up to eight BAs in organic and fair trade cocoa-based products without the need of the derivatization step with time saving and with good values of recovery and precision ( Restuccia et al., 2016;Spizzirri et al., 2016a,b). ...
... This pointed out a new "thermogenic" BAs formation. This effect was recently underlined during cocoa beans roasting (Oracz and Nebesny, 2014), although the temperatures involved (110-150°C) were quite different from those applied during coffee thermal treatment. Strecker degradation seems to be responsible for the formation of BAs by thermal decarboxylation of amino acids in the presence of α-dicarbonyl compounds formed during the Maillard reaction ( Granvogl et al., 2006) or lipid peroxidation products . ...
... Also tea, coffee, and cocoa, as well as their derivatives, have been considered as a source of BAs, although few studies are present in the literature, mainly regarding raw materials (Cirilo et al., 2003;Casal et al., 2004;Vasconcelos et al., 2007;Palavan-Unsal et al., 2007;Oracz and Nebesny, 2014). Profiles and concentrations are reported to be very much varied as these molecules can be formed/accumulated in relation with the type and quality of raw materials, their origin and processing which in turn is driven by manufacturing technology, agronomic conditions, trading, blend, storage, and distribution of these commodities (Dias et al., 2012;Zhang et al., 2014;Restuccia et al., 2016;CarmoBrito et al., 2017). ...
... In this way, UHPLC allows excellent separations in shorter analysis time compared to those obtained by conventional LC. However, the direct separation of BAs is difficult in reversed-phase mode so that precolumn derivatization has usually been performed in UHPLC methods (Oracz and Nebesny, 2014). Finally, LC-ELSD methodology showed accurate and precise determination of up to eight BAs in organic and fair trade cocoa-based products without the need of the derivatization step with time saving and with good values of recovery and precision Spizzirri et al., 2016a,b). ...
... This pointed out a new "thermogenic" BAs formation. This effect was recently underlined during cocoa beans roasting (Oracz and Nebesny, 2014), although the temperatures involved (110-150°C) were quite different from those applied during coffee thermal treatment. Strecker degradation seems to be responsible for the formation of BAs by thermal decarboxylation of amino acids in the presence of α-dicarbonyl compounds formed during the Maillard reaction (Granvogl et al., 2006) or lipid peroxidation products . ...
... Cocoa's health benefits stem from its complex composition and intense processing, involving biogenic amines, polyphenols, methylxanthines, and their interactions [3]. Biogenic amines (BAs) in cocoa, such as polyamines, histamine, tyramine, dopamine, serotonin, and salsolinol, can naturally occur or form during processing through microbial/oxidative decarboxylation, amination, transamination, thermal decarboxylation, or lipid peroxidation [4][5][6]. While some BAs are beneficial at low levels, high intake or their interaction with drugs, alcohol, or polyamines can be harmful [7,8]. ...
... The cocoa powder samples were rich in SER and DOP, with their results at very high levels, confirming the data from the literature [6,47,48]. Dopamine and serotonin are neurotransmitters that play an important role in the brain's reward system. DOP is involved in motivation, the reinforcement of behaviors, and pleasure; SER is a calming neurotransmitter. ...
Article
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Cocoa (Theobroma cacao, L.) represents an important market that gained relevance and became an esteemed commodity thanks to cocoa powder, chocolate, and other related products. This work analyzed 59 cocoa powder samples from the European market. Three distinct subgroups were identified: organic or conventional, alkalized or not alkalized, and raw or roasted processing. The impact of the technological process on their pH, color, and compositional traits, as well as their content of biogenic amines and salsolinol, was evaluated. The phenolic fraction was also investigated through both common and emerging methods. The results depict that the influence of the agronomical practices (organic/conventional) did not significantly (p < 0.05) affect the composition of the cocoa powders; similarly, the roasting process was not a determinant of the compounds traced. On the other hand, the alkalinization process greatly impacted color and pH, no matter the cocoa’s provenience or obtention or other processes, also resulting in reducing the phenolic fraction of the treated samples. Principal component analysis confirmed that the alkali process acts on pH, color, and phenolic composition but not on the content of other bioactive molecules (biogenic amines and salsolinol). All the samples were safe, while the alkalized powders saw a great reduction in beneficial biocompounds. A novel strategy could be to emphasize on the label whether cocoa powder is non-alkalized to meet the demand for more beneficial products.
... Baking increased the tyramine and histam contents, reaching 13.73 and 14.76 mg/kg, respectively. Similarly, in the roasting pro of cocoa beans, it was found that higher temperatures resulted in the highest increa BAs due to the thermal decarboxylation of amino acids during heat treatment [39] other previous study [40] on soybean paste also reported that roasting was identified factor contributing to the elevation of BA content. Unlike tyramine and histamine, both cadaverine and putrescine are considere exhibit less toxicity; however, the major issue related to these amines is the potentia of the toxicity of other amines, especially histamine. ...
... Baking increased the tyramine and histamine contents, reaching 13.73 and 14.76 mg/kg, respectively. Similarly, in the roasting process of cocoa beans, it was found that higher temperatures resulted in the highest increase in BAs due to the thermal decarboxylation of amino acids during heat treatment [39]. Another previous study [40] on soybean paste also reported that roasting was identified as a factor contributing to the elevation of BA content. ...
Article
Full-text available
This study investigated the safety and functionality of traditional African sourdough flatbread (kisra), based on the content of biogenic amines (BAs) and antioxidant compounds and their improvement using lactic acid bacteria (LAB) species. The primary BAs detected in naturally fermented kisra were tyramine, histamine, putrescine, and cadaverine, with putrescine being the most abundant after baking. In vitro BA production of microorganisms isolated from kisra sourdough revealed that the Enterococcus genus contributed to tyramine accumulation, whereas presumptive yeasts may contribute to putrescine and cadaverine accumulation. The use of LAB species, including Lactiplantibacillus plantarum, Limosilactobacillus fermentum, Levilactobacillus brevis, and Weissella cibaria, significantly reduced putrescine content to less than about 23% of that of naturally fermented kisra, and eliminated tyramine, histamine, and cadaverine formation. Meanwhile, DPPH scavenging activity, total polyphenolic content, and tannin content in naturally fermented kisra were 85.16%, 1386.50 µg/g, and 33.16 µg/g, respectively. The use of LAB species did not affect the DPPH scavenging activity or tannin content but significantly increased the total phenolic content by up to 20% compared to naturally fermented kisra. Therefore, fermentation with LAB starter cultures might be a promising approach to improve the safety related to BAs as well as the functionality of kisra bread.
... In addition, factors such as temperature, fermentation strain and mode, free amino acid content, salt concentration, and pH can also affect the synthesis of BAs in foods [13][14][15]. Oracz and Nebesny indicated that the content of BAs in cocoa beans increases with the increasing roasting temperature (110 • C to 150 • C) and air humidity (0.3% to 5.0%) [16]. Therefore, inhibiting the formation of BAs in foods by reducing free amino acid contents, limiting the growth of amine-positive microorganisms, and changing food processing conditions and additives has become a research focus [17,18]. ...
... The results of BA detection showed that the contents of ETM, PEM, and HIM in green tea reached 516.07 µg/g, 25.85 µg/g, and 73.22 µg/g, increased by 656.4%, 211.1%, and 164.2% compared with those of the original leaves, respectively ( Figure 2 and Table S1). Similarly, previous studies have also shown that the levels of BAs such as PEM, HIM, and TYM in coffee and cocoa beans would significantly increase after hightemperature treatment [16,38]. Meanwhile, two new BAs, PYN (47.03 µg/g) and PTN (36.14 µg/g), were synthesized in the process of producing green tea. ...
Article
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This study aimed to evaluate the effects of processing methods on the content of biogenic amines in Zijuan tea by using derivatization and hot trichloroacetic acid extraction with HPLC-UV. The results showed that the most abundant biogenic amine in the original leaves was butylamine, followed by ethylamine, methylamine, 1,7-diaminoheptane, histamine, tyramine, and 2-phenethylamine. However, during the process of producing green tea, white tea, and black tea, the content of ethylamine increased sharply, which directly led to their total contents of biogenic amines increasing by 184.4%, 169.3%, and 178.7% compared with that of the original leaves, respectively. Unexpectedly, the contents of methylamine, ethylamine, butylamine, and tyramine in dark tea were significantly reduced compared with those of the original leaves. Accordingly, the total content of biogenic amines in dark tea was only 161.19 μg/g, a reduction of 47.2% compared with that of the original leaves, indicating that the pile-fermentation process could significantly degrade the biogenic amines present in dark tea.
... Salsolinol and biogenic amines are minor alkaloids that do not affect the cocoa flavor, whereas they may contribute to the psychopharmacological activity (Tuenter et al., 2018). However, consumption of those compounds in high concentration may cause undesirable physiological and/or toxicological problems (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). The levels of the biogenic amines mainly depend on the thermal bean processing, such as roasting (Oracz & Nebesny, 2014), whereas there is no information regarding the impact of alkalization. ...
... However, consumption of those compounds in high concentration may cause undesirable physiological and/or toxicological problems (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). The levels of the biogenic amines mainly depend on the thermal bean processing, such as roasting (Oracz & Nebesny, 2014), whereas there is no information regarding the impact of alkalization. ...
Article
Alkalization is a process to improve color, dispersibility and flavor of cocoa powder but is likely to have a negative effect on the phytochemicals. Hereto, the impact of alkalization degree (none, medium and high) on the potential mood-enhancing compounds corresponding to the four levels of the mood pyramid model (flavanols, methylxanthines, biogenic amines and orosensory properties) was investigated. The phytochemical content, analyzed via UPLC-HRMS, showed reduction of specific potential mood-enhancing compounds upon alkalization, implying a decrease in bitterness and astringency. Moreover, volatile compounds analysis via HS-SPME-GC-MS indicated that alkalization reduced the levels of volatile compounds, responsible for acidity, fruity, floral and cocoa aromas. With respect to the orosensory properties, the cocoa powder palatability was suggested to be increased due to reduced acidity, bitterness, and astringency, while the desired volatile compounds were reduced. However, sensorial analysis is required to link the volatile results with the overall effect on the flavor perception.
... Increased roasting time or temperature of a roasting treatment resulted in a decreased levels of these molecules, as expected from previous research (Pinto & Chichester, 1966). Both L-tyrosine and L-α-phenylalanine diminished with more than 80% when applying a roasting treatment at 160°C for 30 min, compared to the non-roasted sample ( (Oracz & Nebesny, 2014). A diminution of 5-hydroxy-dL-tryptophan (5-HTP) during roasting could be expected, as this compound can degrade to serotonin after thermal decarboxylation; moreover, it is sensitive to oxidation (Martins & Gloria, 2010). ...
... With regard to the amino acids (L-tryptophan, L-tyrosine, L-α-phenylalanine) and biogenic amines (tryptamine, tyramine, 2-phenylethylamine and salsolinol), no signi cant di erences (p > 0.05) were found either, except for serotonin, which was more abundant in the CR chocolate, compared to the MR2 chocolate. One type of reaction which can occur during roasting is the decarboxylation of amino acids, resulting in formation of the corresponding biogenic amines (Oracz & Nebesny, 2014). Since the levels of amino acids and biogenic amines in general did not di er signi cantly, the CR and MR had a comparable impact on these compounds and decarboxyla-5.3. ...
Book
Roasting plays a critical role in the production process of cocoa liquor and chocolate. Besides desirable changes in color and moisture content, flavor development is one of the most important reasons to roast cocoa. By means of a convective and/or conductive heat transfer, cocoa and nutty flavors are generated within the roasted beans, while the bitter taste and astringent mouthfeel are reduced. Roasting via a convective and/or conductive heat transfer is easy applicable and therefore also commonly used. However, these roasting techniques are lately questioned due to the long roasting times needed to sufficiently heat the core of the beans. Therefore, a growing interest is encountered to search for optimal roasting conditions and/or alternative roasting techniques, with the development of a desirable flavor profile as primary criterion. Within this research a comparison was made between conventional and microwave-assisted roasting with the main focus on flavor. The impact of varying roasting conditions (i.e. time, temperature and power input) on the flavor profile of cocoa liquor and chocolate was investigated via both instrumental (i.e. HS-SPME-GC-MS, UPLC-HRMS) and sensory (i.e. trained panel, consumer panel) techniques. Results confirmed that microwave-assisted roasting has the potential to be used as alternative technique.
... In addition, naturally occurring microorganisms such as yeasts, filamentous fungi, LAB and AAB, are able to hydrolyze the proteins present in cocoa beans, thus providing FAA to the BA synthesis [10] or the production of fusel alcohols, acids and esters. Although many factors influence decarboxylase activity, this is amplified at low pH values, as a protection mechanism of bacteria against the acid medium [11]. In general, LAB is the most important biogenic amine producers in fermented foods [9], in spite of other less studied microorganisms like Enterobacteriaceae, Pseudomonads, Clostridium perfringens and yeasts. ...
... Sample preparation was performed according to the methods reported by [11] with slight modifications. Briefly, one gram of sample was defatted through three successive washes with 5 mL of hexane (3 × 5 mL), and then defatted samples were dried under nitrogen. ...
Article
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Yeast starters for cocoa fermentation are usually tested according to their enzymatic activities in terms of mucilage degradation and flavor improvement, disregarding their influence on the production or elimination of toxic compounds as biogenic amines (BAs), important for human health. In this work, we tested 145 strains belonging to 12 different yeast species and isolated from the Colombian fermented cocoa beans (CB) for their capability of producing BAs in vitro. Sixty-five strains were able to decarboxylate at least one of the amino acids tested. Pichia kudriavzevii ECA33 (Pk) and Saccharomyces cerevisiae 4 (Sc) were selected to evaluate their potential to modulate BAs, organic acids, and volatile organic compounds (VOCs) accumulation during a simulated cocoa fermentation. The growth of Sc or Pk in the presence of CB caused a significant reduction (p < 0.05) of 2-phenylethylamine (84% and 37%) and cadaverine (58% and 51%), and a significant increase of tryptamine and putrescine with a strong influence of temperature in BA formation and degradation. In addition, our findings pointed out that Pk induced a major production of fatty acid- and amino acid-derived VOCs, while Sc induced more VOCs derived from fatty acids metabolism. Our results suggest the importance of considering BA production in the choice of yeast starters for cocoa fermentation.
... there can be decreases on total, spermidine, tryptamine, tyramine and serotonin contents, and the production and accumulation of 2-phenylethylamine (Gloria, Deus, & Franca, 2019). During cocoa roasting, there can be lipid oxidation, Maillard reaction and thermal decarboxylation of amino acids with formation of amines, including 2-phenylethylamine (Oracz & Nebesny, 2014), spermine (Delgado-Ospina et al., 2020) and tryptamine (Oracz & Nebesny, 2014). However, there can also be degradation of some bioactive amines, e.g. ...
... there can be decreases on total, spermidine, tryptamine, tyramine and serotonin contents, and the production and accumulation of 2-phenylethylamine (Gloria, Deus, & Franca, 2019). During cocoa roasting, there can be lipid oxidation, Maillard reaction and thermal decarboxylation of amino acids with formation of amines, including 2-phenylethylamine (Oracz & Nebesny, 2014), spermine (Delgado-Ospina et al., 2020) and tryptamine (Oracz & Nebesny, 2014). However, there can also be degradation of some bioactive amines, e.g. ...
Article
Chocolate is an important source of free bioactive amines and amino acids which play important roles in human health. Considering the limited information on the bioaccessibility of these compounds from chocolate, the objective of this study was to characterize their profiles and bioaccessibility in 70% cocoa dark chocolate through in vitro simulation of oral, gastric and intestinal digestions. Seven amines were detected; polyamines were predominant before in vitro digestion, whereas tyramine, cadaverine and spermidine after digestion. All amines showed high bioaccessibility with slight influence of digestive enzymes. Amines increased after gastrointestinal digestion: tyramine (13-fold), tryptamine (9-fold), others (2.4–4.2-fold) and histamine appeared. All amino acids, GABA and ammonia were detected in chocolate, and their contents increased after in vitro digestion due to digestive enzymes (4.6, 2.8 and 2.1, respectively). Dark chocolate protein is a good source of tryptophan, phenylalanine + tyrosine, isoleucine, histidine, but limiting for lysine, leucine, and threonine. https://doi.org/10.1016/j.foodchem.2020.128397 Anyone clicking on this link before February 16, 2021 will be taken directly to the final version of your article on ScienceDirect, which they are welcome to read or download: https://www.sciencedirect.com/science/article/pii/S0308814620322597
... mg/kg) were detected in P. kudriavzevii treatments (Pk and ScPk), suggesting that this yeast can be associated with the buildup of this amine. Furthermore, phenylethylamine can be formed during cocoa dehydration, due to release from conjugated amines or to the oxidative decarboxylation of the precursor amino acid (phenylalanine) at high temperatures (Oracz & Nebesny, 2014). Phenylethylamine is an important hypothalamic stimulating amine and, thus, can induce feelings of well-being and affect the levels of serotonin and brain endorphins, improving mood (Afoakwa, 2008). ...
... Phenylethylamine is an important hypothalamic stimulating amine and, thus, can induce feelings of well-being and affect the levels of serotonin and brain endorphins, improving mood (Afoakwa, 2008). But at high levels (≥30 mg/kg), this amine can be detrimental to human health, inducing migraines (Oracz & Nebesny, 2014;Jeon, Lee, & Mah, 2018). The levels of phenylethylamine obtained with the different treatments are far below the values capable of causing adverse effect to human health. ...
Article
The use of starters during fermentation has been gaining momentum as it can warrant high-quality chocolate. The objective of this study was to investigate the influence of Saccharomyces cerevisiae (Sc) and Pichia kudriavzevii (Pk) during on-farm fermentation on physico-chemical and microbiological characteristics and levels of methylxanthines and bioactive amines of cocoa. Four treatments were used: ScPk (1:1), only Sc, only Pk, and no starter (control). The starters lead to changes throughout fermentation, but provided fermented cocoa with similar pH, titratable acidity, reducing sugars and phenolic compounds. ScPk shortened fermentation time by 24 h. The ScPk fermented and dried cocoa had higher levels of monomeric phenols, methylxanthines, phenylethylamine and lower levels of the putrefactive amines – putrescine and cadaverine (p<0.05). The results were confirmed by multivariate analysis. Based on these results, the mixture of both yeasts species is a promising starter for cocoa fermentation decreasing duration time and modulating high-quality components.
... Free tryptophan (which can be present as protein-bound as well), is transformed during fermentation into biogenic amines (5-hydroxytryptamine and tryptamine) [9]. Although the exact mechanism of tryptamine formation in cocoa beans has not been revealed, Oracz and Nebesny [14] proposed a mechanism of its enzymatic formation from tryptophan ( Figure 1) and do Carmo Brito et al. [15] reported that the level of tryptamine decreases in the first four days of fermentation, only to slowly increase to virtually the same level by the sixth day. The presence of small amounts of tryptamine in raw cocoa beans has also been reported, as well as differences regarding variety (due to different composition of the bean) and origin (due to differences in cultivation conditions and microflora involved in the fermentation process) of cocoa beans [14]. ...
... Although the exact mechanism of tryptamine formation in cocoa beans has not been revealed, Oracz and Nebesny [14] proposed a mechanism of its enzymatic formation from tryptophan ( Figure 1) and do Carmo Brito et al. [15] reported that the level of tryptamine decreases in the first four days of fermentation, only to slowly increase to virtually the same level by the sixth day. The presence of small amounts of tryptamine in raw cocoa beans has also been reported, as well as differences regarding variety (due to different composition of the bean) and origin (due to differences in cultivation conditions and microflora involved in the fermentation process) of cocoa beans [14]. Therefore, it is yet to be revealed whether the process of tryptamine synthesis from tryptophan is spontaneous, or whether endogenous enzymes or enzymes of microflora during fermentation are involved. ...
Article
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Chocolate production is a complex process during which numerous chemical reactions occur. The most important processes, involving most of the reactions important for development of the proper chocolate flavor, are fermentation, drying and roasting of cocoa bean, and chocolate conching. During fermentation, formation of important precursors occurs, which are essential for further chemical reactions in the following processes of chocolate production. Roasting is one of the most important processes due to the occurrence of Maillard’s reactions, during which aroma compounds are formed. In this paper, we have reviewed the most important chemical reactions that occur with proteins, carbohydrates, lipids, and polyphenols. Additionally, we present other components that may be naturally present or form during the production process, such as methylxanthines, aldehydes, esters, ketones, pyrazines, acids, and alcohols.
... Cocoa beans also contain a further interesting group of compounds arising from the enzymatic and/or (chemical) decarboxylation of amino acids representing bioactive amines, where mainly 2-phenylethylamine, tyramine, tryptamine, serotonin and dopamine are found [118][119][120]. Cocoa can also be a source of polyamines (spermidine and spermine), which may also contribute to cocoa's antioxidant activity [118]. ...
... The changes in bioactive amines may be partly attributed through amino acid decarboxylation by microbial enzymes during the fermentation process of cocoa beans and their fate has been discussed in [118]. The roasting process also modifies significantly the profile and levels of biogenic amines [120]. ...
Article
The protein fractions of cocoa have been implicated influencing both the bioactive potential and sensory properties of cocoa and cocoa products. The objective of the present review is to show the impact of different stages of cultivation and processing with regard to the changes induced in the protein fractions. Special focus has been laid on the major seed storage proteins throughout the different stages of processing. The study starts with classical introduction of the extraction and the characterization methods used, while addressing classification approaches of cocoa proteins evolved during the timeline. The changes in protein composition during ripening and maturation of cocoa seeds, together with the possible modifications during the post-harvest processing (fermentation, drying, and roasting), have been documented. Finally, the bioactive potential arising directly or indirectly from cocoa proteins has been elucidated. The “state of the art” suggests that exploration of other potentially bioactive components in cocoa needs to be undertaken, while considering the complexity of reaction products occurring during the roasting phase of the post-harvest processing. Finally, the utilization of partially processed cocoa beans (e.g., fermented, conciliatory thermal treatment) can be recommended, providing a large reservoir of bioactive potentials arising from the protein components that could be instrumented in functionalizing foods.
... Makhamrueang et al. observed that blanching and boiling elevated the levels of biogenic amines in undried Hericium erinaceus samples, in addition to aquatic products (Makhamrueang et al., 2021). The explanation of the increase of biogenic amines formation with the application of high temperature culinary treatments can be explained by greater rise of precursor transformation at high heat treatment (Oracz, Nebesny, 2014;Kim et al., 2021). Fatty food during the heat treatment releases lipid peroxides that influences chemical decarboxylation of amino acids (Zamora et al., 2012). ...
Article
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This study examines the amino acid composition and biogenic amine formation in common carp (Cyprinus carpio) meat subjected to baking and frozen storage for one and three months. Amino acids were analyzed using cation-exchanged liquid chromatography in hydrolysates, while biogenic amines were determined via reverse-phase high-performance liquid chromatography with pre-column derivatization using dansyl chloride. The analysis focused on 15 amino acids, with glutamic acid being the most abundant and tyrosine the least present in both fresh and baked samples. The total amino acid content decreased from 364.5 g/kg DW in fresh carp meat to 314.2 g/kg DW in baked samples. Biogenic amines, organic compounds formed through amino acid breakdown, were also evaluated due to their implications for food quality and consumer health. Four biogenic amines—2-phenylethylamine, putrescine, spermidine, and spermine—were detected. Their levels increased in the following order: fresh meat < frozen meat (1 month) < frozen meat (3 months) < baked meat. Initial concentrations of putrescine (2.80 mg/kg DW) and spermidine (15.23 mg/kg DW) in fresh carp meat rose significantly after freezing and baking, with spermine also detected after one month of storage. Tyramine levels increased significantly in baked samples. Statistical analysis using Tukey’s test showed significant differences (p<0.05) among the variables under described experimental conditions, indicating the need for further studies to monitor biogenic amine trends in processed freshwater fish products.
... Oracz and Nebesny [23] found that tyramine was the most prevalent in raw cocoa beans, but roasted cocoa beans had higher levels of 2-phenylethylamine. Roasting increases BA concentrations, with temperature and humidity being key factors. ...
Article
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Cocoa and chocolate are known for their health benefits, which depend on factors like cocoa variety, post-harvest practices, and manufacturing processes, including fermentation, drying, roasting, grinding, and refining. These processing methods can influence the concentration and bioavailability of bioactive compounds, such as polyphenols that are linked to cardiovascular health and antioxidant effects. Recent scientific research has led to the development of cocoa-based products marketed as functional foods. However, despite the growing interest in the functional potential of cocoa, the literature lacks crucial information about the properties of different varieties of cocoa and their possible implications for human health. Moreover, climate change is affecting global cocoa production, potentially altering product composition and health-related characteristics. In addition to polyphenols, other compounds of interest are biogenic amines, due to their role and potential toxic effects on human health. Based on toxicological data and recent research on the complex relationship between biogenic amines and cocoa fermentation, setting limits or standards for biogenic amines in cocoa and chocolate could help ensure product safety. Finally, new trends in research on biogenic amines in chocolate suggest that these compounds might also be used as quality markers, and that product formulation and process conditions could change content and diversity of the different amines.
... Drying is an important step which affects the quality characteristic of cocoa bean during industrial processing. (8). Drying of cocoa beans before winnowing is very crucial because it makes the beans amenable to fracture easily, thereby releasing the much desired nibs from the shells. ...
Article
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It's a concept for the design of a hybrid Cocoa roasting and winnowing machine for small scale Cocoa processors in Nigeria using local technology.
... The cocoa tree Theobroma cacao is grown in large areas in tropical countries. Processed beans manufacture cocoa powder, an ingredient widely used by the food industry (Belscak et al., 2009;Oracz and Nebesny, 2014). As for other plant foods, contamination of cocoa beans and derived products by sporeforming bacteria is almost impossible to avoid. ...
... This was reflected in their increasing trend with a decreasing cocoa pulp-bean mass pH. An increase of the concentrations of these biogenic amines in cocoa beans has been described before (Oracz and Nebesny, 2014;De Brito et al., 2017). The low tryptamine and tyramine concentrations in the cocoa beans of the AFSC VII and AFSC VIII fermentation processes may be associated with the ability of S. cerevisiae and P. kudriavzevii to degrade biogenic amines in the cocoa pulp (Delgado-Ospina et al., 2021). ...
Article
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The microbiological and metabolic outcomes of good cocoa fermentation practices can be standardized and influenced through the addition of starter culture mixtures composed of yeast and bacterial strains. The present study performed two spontaneous and 10 starter culture-initiated (SCI) cocoa fermentation processes (CFPs) in Costa Rica with local Trinitario cocoa. The yeast strains Saccharomyces cerevisiae IMDO 050523, Hanseniaspora opuntiae IMDO 020003, and Pichia kudriavzevii IMDO 060005 were used to compose starter culture mixtures in combination with the lactic acid bacterium strain Limosilactobacillus fermentum IMDO 0611222 and the acetic acid bacterium strain Acetobacter pasteurianus IMDO 0506386. The microbial community and metabolite dynamics of the cocoa pulp-bean mass fermentation, the metabolite dynamics of the drying cocoa beans, and the volatile organic compound (VOC) profiles of the chocolate production were assessed. An amplicon sequence variant approach based on full-length 16S rRNA gene sequencing instead of targeting the V4 region led to a highly accurate monitoring of the starter culture strains added, in particular the Liml. fermentum IMDO 0611222 strain. The latter strain always prevailed over the background lactic acid bacteria. A similar approach, based on the internal transcribed spacer (ITS1) region of the fungal rRNA transcribed unit, was used for yeast strain monitoring. The SCI CFPs evolved faster when compared to the spontaneous ones. Moreover, the yeast strains applied did have an impact. The presence of S. cerevisiae IMDO 050523 was necessary for successful fermentation of the cocoa pulp-bean mass, which was characterized by the production of higher alcohols and esters. In contrast, the inoculation of H. opuntiae IMDO 020003 as the sole yeast strain led to underfermentation and a poor VOC profile, mainly due to its low competitiveness. The P. kudriavzevii IMDO 060005 strain tested in the present study did not contribute to a richer VOC profile. Although differences in VOCs could be revealed in the cocoa liquors, no significant effect on the final chocolates could be obtained, mainly due to a great impact of cocoa liquor processing during chocolate-making. Hence, optimization of the starter culture mixture and cocoa liquor processing seem to be of pivotal importance.
... The volatile acids such as acetic acid are reduced as a result of roasting at high temperature. Meanwhile, the less volatile acids (citric, oxalic, succinic, tartaric and lactic) unchanged (Afoakwa et al., 2008, Frauendorfer & Schieberle, 2008, Oracz & Nebesny, 2014. ...
... This profile differs from that of Brazilian commercial 70 % cocoa chocolate, in which the polyamines (spermidine and spermine) were prevalent (22 %), followed by 2-phenylethylamine, cadaverine and putrescine (~15 %) (Dala-Paula et al., 2021a), and also from chocolates made with different Brazilian cocoa clones (Deus et al., 2020). Therefore, these results reinforce the influence of cocoa cultivar and processing on the levels and profile of amines in the chocolate (Oracz & Nebesny, 2014;Restuccia et al., 2016;Deus et al., 2020). ...
Article
The influence of under-fermented (UF) cocoa (0 to 65 %) on bioactive amines in chocolate and their in vitro bioaccessibility was investigated. The same amines were found in all treatments; however, treatments were divided into two groups regarding total amines [0 & 20 % UF (34 mg/kg) and 35 to 65 % UF (17 mg/kg)] and phenolic levels [lower and higher, respectively]. Serotonin, tyramine, putrescine, cadaverine, agmatine and phenylethylamine were higher in chocolate with ≤ 20 % UF cocoa. Histamine and spermidine were not affected. Digestibility studies indicated that low levels of amines were present in the oral phase. Gastric digestion was effective in releasing tyramine, spermidine and phenylethylamine from conjugates. Serotonin and agmatine were not detected after in vitro digestion of chocolate with ≥ 35 % UF cocoa. Histamine was released during in vitro intestinal digestion. By adding different proportions of UF cocoa during chocolate production, the levels and bioaccessibility of amines can be modulated.
... Alternatively, amino acids can undergo decarboxylation, resulting in the formation of biogenic amines. Few papers report on the biogenic amine contents of cocoa beans, cocoa liquors, or chocolates (do Carmo Brito et al., 2017;Oracz and Nebesny, 2014;Tuenter et al., 2020), and factors influencing their levels are still rather unclear. During fermentation, biogenic amines can be expected to be formed, although to a lesser extent compared to the roasting step (Barišić et al., 2020;Tuenter et al., 2020). ...
Article
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Hanseniaspora opuntiae is a commonly found yeast species in naturally fermenting cocoa pulp-bean mass, which needed in-depth investigation. The present study aimed at examining effects of the cocoa isolate H. opuntiae IMDO 040108 as part of three different starter culture mixtures compared with spontaneous fermentation, regarding microbial community, substrate consumption, and metabolite production dynamics, including volatile organic compound (VOC) and phytochemical compositions, as well as compositions of the cocoa beans after fermentation, cocoa liquors, and chocolates. The inoculated H. opuntiae strain was unable to prevail over background yeasts present in the fermenting cocoa pulp-bean mass. It led to under-fermented cocoa beans after four days of fermentation, which was however reflected in higher levels of polyphenols. Cocoa fermentation processes inoculated with a Saccharomyces cerevisiae strain enhanced flavour production during the fermentation and drying steps, which was reflected in richer and more reproducible aroma profiles of the cocoa liquors and chocolates. Finally, sensory analysis of the cocoa liquors and chocolates further demonstrated that S. cerevisiae led to more acidic notes compared to spontaneous fermentation, as a result of an advanced fermentation degree. Finally, different VOC profiles were found in the cocoa beans throughout the whole chocolate production chain, depending on the fermentation process.
... During roasting non-volatile compounds that do not participate on cacao flavor development are also produced. Some of these compounds are biogenic amines such as 2-phenylethylamine, tyramine, tryptamine, serotonin, and dopamine, which have a vital role in the mood-enhancing effect cacao (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). ...
Chapter
Chocolate production implies an extensive post-harvest process of the cacao beans, the seeds of the tree Theobroma cacao L. All the steps from bean harvesting into the chocolate bar’s obtention (cocoa origin, composition and manufacturing procedure) will affect chocolate properties, providing to the final product unique sensory qualities that will attract consumers. Cocoa products are worldwide consumed because they are recognized as a significant source of polyphenols, molecules with essential health benefits. The current consumers’ concern about their wellness leads them to change the purchasing behavior and looking for new beneficial health-related products. In this context, and in addition to its sensorial properties chocolate rich in cacao content is an exceptional carrier to deliver bioactive compounds such as flavonoids, tannins, peptides, fiber, and some probiotics among others; making the chocolate a good healthy product. For this reason, this chapter aims to provide an update on the harvesting, post-harvest handling of cacao, chocolate manufacturing, and how each process impacts the sensorial and functional quality of chocolate.KeywordsCacao beanChocolateEpicatechinMethylxanthinesMood
... These amino acids can then be enzymatically decarboxylated by some microorganisms forming amines (Granvogl et al., 2006). The low pH value favours the decarboxylase activity during fermentation, associated with a defence mechanism developed by microorganisms to protect themselves from acidic environments (Gloria et al., 2005;Oracz and Nebesny, 2014). Biogenic amines, even at low levels, are relevant to human health, while some of them can cause adverse effects at high levels. ...
Article
In this work, we determined the degree of filamentous fungi contamination in cocoa fermented seeds and the fungal potential to produce enzymes that could contribute to the cocoa quality. Internal transcribed spacer amplicon sequencing (ITS) showed 11 different species with Byssochlamys spectabilis, Aspergillus niger, Aspergillus flavus, Aspergillus carbonarius, Circinella muscae and Penicillium citrinum as the most abundant species. Our results evidenced intra and inter-species differences in the enzymes production. Cellulases, β-glucosidase, ornithine decarboxylase and phenylalanine decarboxylase were the most diffused enzymes expressed in the 53 strains here studied. Moreover, A. niger (6/12), A. carbonarius (2/3), and P. citrinum (3/3) showed high pectinolytic activity. Remarkable was the amino decarboxylase activity of P. citrinum, and A. flavus strains. For the first time we reported the presence of B. spectabilis in cocoa fermented beans, which could play an important role in the biogenic amines formation. In addition, we explored the capability of the Aspergillus section Nigri strains, to produce ochratoxin A (OTA) in a cacao model system (CPMS) and in malt extract medium (MEL). We observed that CPMS, but not MEL, stimulated the OTA production in 6 out 15 strains of Aspergillus section Nigri, reaching values ranging between 1.70 and 4995 μg OTA kg⁻¹ dry mycelium.
... It is desirable to optimize roasting conditions that maximize the desired compounds' production while preserving a desirable sensory profile. Nevertheless, roasting increases the content of biogenic amines (entry 7), resulting in Trinitario beans the highest final content [104]. The main biogenic amines found are 2-phenylethylamine, Fig. 6 Illustrative diagram of the stages of roasting cocoa in a roaster tyramine, tryptamine, serotonin, dopamine, and histamine [78,105]. ...
Article
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The quality of cocoa depends on both the origin of the cacao and the processing stages. The roasting process is critical because it develops the aroma and flavor, changing the beans’ chemical composition significantly by chemical reactions induced by thermal energy. Aspects have been identified as the main differences between bulk cocoa and fine cocoa, the effect of time and temperature on the formation of the flavor and aroma, and the differences between conductive heating in an oven, convective with airflow, and steam flow. Thermal energy initially causes drying, then non-enzymatic browning chemical reactions (Maillard reaction, Strecker degradation, oxidation of lipids, and polyphenols), which produce volatile and non-volatile chemical compounds related to the flavor and aroma of cocoa roasted. This review identified that the effect of the heating rate on the physicochemical conversion of cocoa is still unknown, and the process has not been evaluated in inert atmospheres, which could drastically influence the avoidance of oxidation reactions. The effect of particle size on the performance of product quality is still unknown. A more in-depth explanation of energy, mass, and chemical kinetic transfer phenomena in roasting is needed to allow a deep understanding of the effect of process parameters. In order to achieve the above challenges, experimentation and modeling under kinetic control (small-scale) are proposed to allow the evaluation of the effects of the process parameters and the development of new roasting technologies in favor of product quality. Therefore, this work seeks to encourage scientists to work under a non-traditional scheme and generate new knowledge.
... Criollo, Trinitario, and Nacional are however defined as highquality ("fine" grade) varieties, Ecuador being the main producer worldwide of "fine" cocoa beans (Afoakwa et al. 2008;Dand 2011a; Exporters-Ecuador National Association of Cocoa 2016; Kongor et al. 2016;Vargas Jentzsch et al. 2016;International Cocoa Organization 2017). Contrary to other varieties, Nacional has a very short fermentation time and yields excellent beans in terms of flavour (Afoakwa et al. 2008;Motamayor et al. 2008;Afoakwa et al. 2011;Dand 2011b;Oracz and Nebesny 2014;Kongor et al. 2016). Pure Nacional cocoa genotypes are currently scarce and most of the orchards use natural hybrids introduced from Trinidad and Venezuela, which forms the Nacional and Trinitario complex (also known as "Arriba" cocoa). ...
Article
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Cocoa presents a high fat content and a unique fatty acid profile defining its technological and nutritional properties. This study evaluated the fat content and fatty acid composition of Nacional cocoas, a worldwide recognised "fine" variety, collected in 85 Ecuadorian farms while taking into account 3 geographical levels (region, province, and canton). The total fat content varied from 45.61 ± 1.27 to 52.13 ± 0.58 g/100 g DW and was higher in the provinces and cantons from the Amazonian region than in those from the Pacific Coast region. A remarkable effect of the region and the province was shown on the content of individual fatty acids of Nacional cocoa beans. Total amounts of saturated and unsaturated fatty acids also depended on the growing area. Multivariate analysis provided a comprehensive assessment of the cocoa fat composition according to the origin, which may be useful for the selection of cocoas with specific technological and nutritional characteristics. ARTICLE HISTORY
... During cocoa roasting, increased levels of phenylethylamine, tyramine, tryptamine, dopamine, and serotonin were observed and the increase correlated positively with temperature (110 CÀ150 C) and air humidity (0.3%À5.0%). There can also be loss of some amines (putrescine and cadaverine) due to volatilization (Gloria and Engeseth, 2019a,b;Oracz and Nebesny, 2014;Özdestan, 2014;Restuccia et al., 2015). p0610 During germination, there can be formation of biogenic amines due to the physiological changes in the tissues. ...
Chapter
Since the early 1960s, a series of potentially mutagenic and carcinogenic xenobiotics have been identified in foods, resulting from chemical changes induced by processing. The toxic effects have been extensively studied and demonstrated in experimental animals and human cells and tissues; human clinical and epidemiological studies, however, are lacking. Chapter 10 features eight types of such potentially harmful substances (i.e., acrylamide, benzene, biogenic amines, ethyl carbamate, furan and methylfurans, heterocyclic aromatic amines, 3–MCPD and 3–MCPD esters, and nitrosamines). For each one, their chemical structures, occurrence in foods, mechanisms of formation, influencing factors, mitigating strategies, and toxicological aspects are discussed. With the exception of certain biogenic amines, which have some health benefits, and furan, which contributes to the typical aroma of certain foodstuffs (e,g., roasted coffee), substances herein addressed are known for their possible detrimental effects on health. Efforts have been made to minimize their formation, principally by improving the processing and home preparation methods. However, care should be taken that mitigation strategies do not undermine microbial safety and desirable sensory properties.
... For obtaining chocolate from cocoa beans, one very important stage in the process is the roasting [4], which results in the production of desirable flavor and aroma compounds, as well as color changes [5]. The temperature and duration of roasting substantially affected the character in chemical and physical changes of cocoa beans [6]. ...
Article
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Cocoa beans are the main raw material for the manufacture of chocolate and are currentlygaining great importance due to their antioxidant potential attributed to the total phenolic content(TPC) and the monomeric flavan-3-ols (epicatechin and catechin). The objective of this study was todetermine the degradation kinetics parameters of TPC, epicatechin, and catechin during the roastingprocess of Criollo cocoa for 10, 20, 30, 40, and 50 min at 90, 110, 130, 150, 170, 190, and 200◦C. Theresults showed a lower degradation of TPC (10.98±6.04%) and epicatechin (8.05±3.01%) at 130◦Cand 10 min of roasting, while a total degradation of epicatechin and a 92.29±0.06% degradationof TPC was obtained at 200◦C and 50 min. Reaction rate constant (k) and activation energy (Ea)were 0.02–0.10 min−1and 24.03 J/mol for TPC and 0.02–0.13 min−1and 22.51 J/mol for epicatechin,respectively. Degradation kinetics of TPC and epicatechin showed first-order reactions, while thecatechin showed patterns of formation and degradation
... A roasting treatment at 130°C for 30 min did not significantly affect the concentration of L-tyrosine and L-α-phenylalanine was reduced with 18%, compared to the non-roasted sample. Furthermore, the present study revealed a similar decreasing trend for tryptophan, with only significant lower (p < 0.05) levels measured for the intensive roasted samples at 130°C for 50 min and at 160°C for 30 min, presumably caused by oxidation and decarboxylation (Oracz & Nebesny, 2014). A diminution of 5-hydroxy-DL-tryptophan (5-HTP) during roasting could be expected, as this compound can degrade to serotonin after thermal decarboxylation; moreover, it is sensitive to oxidation (Martins & Gloria, 2010). ...
Article
The mood pyramid of cocoa, which was previously proposed as a new concept, consists of four levels (flavan-3-ols, methylxanthines, minor compounds and orosensory properties). Roasting is a crucial process for flavor development in cocoa but is likely to have a negative impact on the phytochemicals. We investigated the effect of roasting time (10 – 50 min) and temperature (110 – 160 °C) on the potential mood-enhancing compounds corresponding to the distinct mood pyramid levels. Phytochemicals were analyzed using UPLC-HRMS, while the flavor was mapped via aroma (HS-SPME-GC-MS) and generic descriptive analysis (trained panel). Results revealed that roasting at 130 °C for 30 min did not significantly affect the levels of epicatechin, procyanidin B2 and theobromine, while salsolinol significantly increased. Moreover, bitterness and astringency were reduced and the desired cocoa flavor was developed. Thus, through selection of appropriate roasting time and temperature conditions phytochemicals of interest could be retained without comprising the flavor.
... Fermented meat products, such as fermented sausages, attain the highest β-phenylethylamine concentrations (up to 182 mg/kg), with fish and fish products (up to 180 mg/kg), fish sauces (up to 172 mg/kg) close behind. This BA is also found in fermented dairy products, such as cheese (up to 61 mg/kg) [European Food Safety Authority (EFSA), 2011], in alcoholic beverages such as beer (up to 8.4 mg/kg), and in vegetables and vegetable products (up to 9.3 mg/kg) [European Food Safety Authority (EFSA), 2011] including cocoa beans and cocoa-containing foods such as chocolate (Oracz & Nebesny, 2014). The β-phenylethylamine present in cocoa-containing foods is, however, usually the result of thermal processing rather than microbial decarboxylation (Irsfeld, Spadafore, & Pruss, 2013). ...
Article
β-phenylethylamine and tryptamine are biogenic amines (BA) often found in foods. In general, BA are assumed to be toxic and their accumulation in food is not recommended. However, present knowledge regarding the toxicity of β-phenylethylamine and tryptamine is limited; more information is needed if qualitative and quantitative risk assessments of foods are to be successfully conducted. This study describes a real-time analysis of β-phenylethylamine and tryptamine toxicity on a human intestinal epithelial cell line. Both BA caused cell necrosis and apoptosis, although the former was the main mode of action of β-phenylethylamine, and the latter the main mode of action of tryptamine. Only tryptamine was cytotoxic at concentrations found in BA-rich foods. The results presented in this work may contribute to establish legal limits for β-phenylethylamine and tryptamine in food.
... Different techniques have been applied for the analysis of such samples, for example High Performance Liquid Chromatography -Ultraviolet detection (HPLC-UV), or Nuclear Magnetic Resonance (NMR) spectroscopy (Caligiani et al., 2014;Natsume et al., 2000). However, Ultra Performance Liquid Chromatography-High Resolution Mass Spectrometry (UPLC-HRMS) is the preferred technique when analyzing also minor non-volatile constituents, (like biogenic amines, as reported by Oracz and Nebesny (2014)) and is applied in this research. With regard to the volatile compounds, different extraction procedures combined with various analytical techniques were already tested (Counet, Callemien, Ouwerx, & Collin, 2002;Frauendorfer & Schieberle, 2008;Owusu, Petersen, & Heimdal, 2011). ...
Article
Cocoa products are obtained from the seeds of Theobroma cacao L. In this research, cocoa liquor and chocolate produced from cocoa beans from West Africa (Forastero, "bulk" cacao) and Ecuador (Nacional variety, "fine-flavor" cacao), were investigated, using a novel approach in which various analytical techniques are combined in order to obtain in-depth knowledge of the studied cocoa samples. The levels of various classes of primary metabolites were determined and a wide range of secondary metabolites, including volatile organic acids, aldehydes, esters, pyrazines, polyphenols, methylxanthines and biogenic amines, were identified and/or quantified by HS-SPME GC-MS (headspace-solid phase microextraction gas chromatography - mass spectrometry). and UPLC-HRMS (ultra-performance liquid chromatography - high resolution mass spectrometry). Odor Activity Values (OAV) were calculated to assess the contribution of individual volatiles on the final aroma. Various volatile aroma compounds were more abundant in the West African cocoa liquor and chocolate, while the Ecuadorian samples were richer in most quantified non-volatile metabolites. Principal component analysis (PCA) confirmed that the four samples can be clearly distinguished. Alcohols, pyrazines, amino acids and biogenic amines were found to be highly influential in causing this differentiation. The proposed approach can be useful in future studies on more extensive cocoa sample collections, in order to highlight similarities and pinpoint typical differences in chemical composition among these samples.
... The increasing of biogenic amine level during roasting can be due to release of conjugated amines or chemical decarboxylation of amino acids in the presence of α-dicarbonyl compounds. The effect of air humidity on increasing biogenic amine concentration can be more effective heating of the cocoa beans compared to dry air (Oracz & Nebesny, 2014). In another study, there was a significant decrease in serotonin concentration of coffee beans after roasting at 300°C for 6 min whereas coffee beans had more serotonin content after 12 min of roasting compared to coffee beans roasted for 6 min (Cirilo et al., 2003). ...
... One of the basic technological operation in cocoa bean processing affecting the quality of cocoa derivative products is roasting (Oracz & Nebesny, 2014). It determines the character of the chemical and physical processes that occurred inside the beans, and the final products quality (Wieslawa Krysiak & Motyl-Patelska, 2006). ...
Article
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This study aimed to measure the effect of roasting time on physicochemical properties and volatile compounds of unfermented cocoa liquor roasted with an oil bath method. Physicochemical properties (pH, temperature, and color), flavor, and volatile compounds were analyzed. The results showed that the longer the roasting time the higher the unfermented cocoa liquor’s temperature, °Hue, and ΔE value, but lower pH and L value. There were 126 volatile compounds obtained by various roasting time, identified as pyrazines (12), aldehydes (16), esters (1), alcohols (31), acids (15), hydrocarbons (11), ketones (19), and others (21). At 15, 20, and 25 minutes of roasting time, 69, 74, and 67 volatile compounds, respectively, were identified. Volatile compounds’ profiles were indicated to be strongly influenced by roasting time. The largest area and highest number of compounds, such as pyrazines and aldehydes, were obtained at 20 minutes, which was also the only time the esters were identified. As well as the time showed a very strong flavor described by panelists.
... These reactions allow new compounds to form, which contributes to the characteristic aroma, taste and colour of chocolate [23,24]. Oracz, et al. [25] stated that during the roasting process, conditions such as time and temperature influence phenolic stability, as well as the characteristics of the obtained taste. ...
Article
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The polyphenol content of cocoa beans and the products derived from them, depend on the regions in which they are grown and the processes to which they are subjected, especially temperature. The aim of the study was to compare the total content of polyphenols and antioxidant activity of chocolates obtained from roasted and unroasted cocoa beans. The chocolates produced from each of the six types of unroasted beans and each of the five types of roasted beans were investigated. The seeds came from Ghana, Venezuela, the Dominican Republic, Colombia and Ecuador. The highest total polyphenol content was determined in cocoa beans originating from Colombia and in the chocolates obtained from them. A higher content of total polyphenols was found in unroasted cocoa beans, which indicates the influence this process had on the studied size. The ability to scavenge free DPPH radicals was at a high level in both the beans and the chocolates produced from them, irrespective of the region where the raw material was grown. A positive correlation between the total polyphenol content and the ability to scavenge free radicals was found.
... Anthocyanins area practical indicator for producers because they allow them to follow the evolution of fermentation in a visual way. In raw cocoas, the content of this type of polyphenols can increase as the intensity of solar radiation increases and in the absence of irrigation during the development of the fruit, as part of a protection mechanism (Beer, 1987;Oracz and Nebesny, 2014). Bajo Cauca is the zone with less rainfall frequency in relation to Uraba and Magdalena Medio, which could induce an oxidative stress in the productive units that did not have an irrigation system, thus generating a higher ratio of anthocyanins (2.12 AE 0.15). ...
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The aim of this study was to compare the quality of a mixture of cocoa harvested and fermented in three subregions of Antioquia (Colombia), from the chemometric profile based on multivariate statistical analysis. A mixture of clones CCN-52, ICS-1, FLE-2, and FEC-2 harvested in Bajo Cauca, Uraba and Magdalena Medio were subjected to a spontaneous fermentation. The characterization of raw and well-fermented cocoa was performed through 38 parameters, and results were compared by a Principal Component Analysis (PCA) and a Cluster Analysis (CA), followed by a Principal Factors Analysis (PFA- CA). The CA showed that there are differences among subregions only in raw cocoa from Bajo Cauca. PCA allowed identifying the variability between raw and fermented cocoa in a representative way and these results were consistent with the chemical profile. Besides, the number of parameters to differentiate raw cocoa from different subregions was reduced (11–13 parameters) and it was possible to characterize well fermented cocoa with only 10 parameters of 38. PFA-CA consolidated in three factors a grouping to identify the cocoa quality according to the process or interest of the sensory or functional properties. Factor 1 (cocoa quality indicators with functional properties), Factor 2 (indicators of quality of the beginning of fermentation) and Factor 3 (indicators of quality of well-fermented cocoa) each one with a weight of 39, 35 and 26 respectively.
... Knowledge of the phenomena that modulate the biochemical reactions that occur during the transformation of cocoa seeds is necessary to establish a control over this bioprocess, based on its proper management to produce cocoa with desired quality characteristics . In this sense, some authors have studied this bioprocess under laboratory conditions to generate a knowledge base as a guide to elucidate the dynamics of flavor formation during cocoa transformation from seeds to beans (John et al. 2016;Eyamo Evina et al. 2016;Kadow et al. 2015;Oracz and Nebesny 2014;Yaw 2014;Amin, Jinap, and Jamilah 1998;Voigt and Biehl 1995;Biehl et al. 1985). These studies are of great relevance for being pioneers in developing methodologies that allow carrying out the cocoa transformation of seeds in a controlled manner. ...
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Chocolate is a widely consumed product worldwide due to its exquisite flavor, which comes from the unique and fascinating cocoa flavor. This flavor depends on little controllable variables such as the genotype and the agroecological niche, and on the other side, on postharvest operations: (1) cocoa transformation from seeds to beans that comprises cocoa seeds preconditioning, fermentation , and drying, and (2) the production of chocolate from the bean in which roasting is highlighted. Postharvest transformation operations are critically important because during these, cocoa flavor is formed, allowing the differentiation of two categories: bulk and specialty cocoa. In this sense, this article presents an overview of cocoa postharvest operations, the variables and phenomena that influence and control the physical and biochemical transformation from seeds to cocoa beans, and their relation to the formation of chocolate flavor. Moreover, research perspectives in terms of control and management of postharvest practices in order to obtain cocoa with differentiated and specialty characteristics "from bean to bar" are discussed.
... Knowledge of the phenomena that modulate the biochemical reactions that occur during the transformation of cocoa seeds is necessary to establish a control over this bioprocess, based on its proper management to produce cocoa with desired quality characteristics . In this sense, some authors have studied this bioprocess under laboratory conditions to generate a knowledge base as a guide to elucidate the dynamics of flavor formation during cocoa transformation from seeds to beans (John et al. 2016;Eyamo Evina et al. 2016;Kadow et al. 2015;Oracz and Nebesny 2014;Yaw 2014;Amin, Jinap, and Jamilah 1998;Voigt and Biehl 1995;Biehl et al. 1985). These studies are of great relevance for being pioneers in developing methodologies that allow carrying out the cocoa transformation of seeds in a controlled manner. ...
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Full-text available
Chocolate is a widely consumed product worldwide due to its exquisite flavor, which comes from the unique and fascinating cocoa flavor. This flavor depends on little controllable variables such as the genotype and the agroecological niche, and on the other side, on postharvest operations: (1) cocoa transformation from seeds to beans that comprises cocoa seeds preconditioning, fermentation, and drying, and (2) the production of chocolate from the bean in which roasting is highlighted. Postharvest transformation operations are critically important because during these, cocoa flavor is formed, allowing the differentiation of two categories: bulk and specialty cocoa. In this sense, this article presents an overview of cocoa postharvest operations, the variables and phenomena that influence and control the physical and biochemical transformation from seeds to cocoa beans, and their relation to the formation of chocolate flavor. Moreover, research perspectives in terms of control and management of postharvest practices in order to obtain cocoa with differentiated and specialty characteristics “from bean to bar” are discussed.
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Sattu is a traditional Indian food product made of chickpea with tremendous nutritional benefits. However, the processing of sattu has not been thoroughly explored which is an impediment to industrial applications involving the development of sattu based products. These products carry immense benefits for consumers and for widespread popularity it is essential that the roasting of sattu for further processing be investigated for improving the properties of sattu while reducing its antinutritional factors. In this work, the impact of sand roasting on the physico-chemical, sensory, antinutritional, thermal, functional and antioxidant properties on sattu were investigated. Chickpea grains were roasted in sand for different time periods (3 to 17 min) and temperature combinations (171 to 228°C). Results revealed that samples treated at 180°C for 15 min had maximum sensory score (3.99) followed by the samples treated at 200°C for 10 min and at 228°C for 10 min. Overall sattu roasted at 180°C for 15 min was found suitable for further application.
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The impact of microwave roasting cocoa beans on the aroma and phytochemical profile of dark chocolates (70% cocoa) was studied. Three chocolates produced from microwave roasted beans (450 W–55 min, 600 W–35 min, 900 W–20 min) were compared with a chocolate produced from convectively roasted beans (130 °C–30 min). Aroma analysis via HS-SPME-GC-MS indicated that microwave roasting of cocoa beans resulted in chocolate with a distinctive aroma profile, compared to the chocolate produced from convectively roasted beans. Increased power input seems the main inducer of elevated levels of aroma compounds. Interestingly, the impact of the four treatments on the phytochemical profile, measured via LC-HRMS, of the chocolates was rather limited. Microwave roasting of cocoa beans was more prone to oxidation, but still within acceptable limits. The results validate that microwave roasting is a promising alternative technique that can be used effectively for chocolate production.
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This study analyses the biogenic amines (BAs) formed in mackerel cooked by various methods and conditions. Five BAs, including tryptamine, β-phenylethylamine, putrescine, histamine, and spermidine, were analysed by high-performance liquid chromatography with UV detection. The level of total BAs was higher in the mackerel fillet (108.14 µg/g) than the headed and gutted fish (91.58 µg/g). Roasted, fried, and stewed mackerel recorded total BA concentrations of 54.28, 82.25, and 163.05 µg/g, respectively. Stewed mackerel contained about 3-fold more BAs than roasted mackerel. The level of total BAs in mackerel increased significantly up to 190%, 236% and 152% as the roasting temperature increased, upon frying, and as stewing temperature increased, respectively (p < 0.05).
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Cocoa (Theobroma cacao L.) is widely cultivated in tropical countries. The cocoa beans are a popular ingredient of confectionery. Cocoa beans contain various chemicals that contribute to their bioactivity and nutritional properties. There has been increasing interest in developing cocoa beans for “healthy” food products. Cocoa beans have special combination of nutrients such as lipids, carbohydrates, proteins and other compounds of biological activities. The bioactive phytochemicals include methylxanthines, polyphenols, biogenic amines, melanoidins, isoprostanoids and oxalates. These phytochemicals of cocoa are related to various in vivo and in vitro biological activities such as antioxidation, anti-cancer, anti-microbial, anti-inflammation, anti-diabetes, cardiovascular protection, physical improvement, anti-photoaging, anti-depression and blood glucose regulation. The potential of bioactive compounds in cocoa remains to be maximized for food and nutritional applications. The current processing technology promotes the degradation of beneficial bioactive compounds, while maximizing the flavors and its precursors. It is not optimized for the utilization of cocoa beans for “healthy” product formulations. Modifications of the current processing line and non-conventional processing are needed to better preserve and utilize the beneficial bioactive compounds in cocoa beans.
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This study investigated the profile of cacao beans from the local Cameroonian Trinitario (SNK) and Forastero (TIKO) in terms of aroma precursors (amino acids and reducing sugars) through fermentation like incubations. Treatments consisted of incubating beans in acetic acid, 100 mmol/L for two days followed by 200 mmol/L of acetic acid for three days (Treatment T1) and in 100 mmol/L of lactic acid for two days followed by 200 mmol/L of acetic acid for three days (Treatment T2). Both treatments resulted in an increase of free amino acids content by 1.5-2.5 times in SNK and TIKO varieties. The ratio of the hydrophobic amino acids over the rest of amino acids showed the preponderance of T1 on the hydrophobic amino acids released in TIKO while in the SNK, some varieties displayed the highest ratio in T2. Glucose and fructose content in TIKO and SNK beans increased 2 to 3 times during incubation. Galactose and raf-finose were found in unfermented beans. After incubation, raffinose was missing while at the same time a raise of galactose content could be seen. These results highlighted that acidification remains the factor inducing the releasing of free hydrophobic amino acids, the genotype being less involved.
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La presente investigación tuvo como objetivo comparar el perfil sensorial de muestras de cacao de varias zonas productoras del país. Con este propósito el Laboratorio de Calidad Integral de Cacao y Chocolate de la Estación Experimental Tropical Pichilingue del INIAP, recibió muestras de 11 asociaciones de productores. Un panel de cinco miembros con experiencia en degustación de pasta de cacao (licor) produjo datos para los siguientes componentes del sabor: cacao, acidez, amargor, astringencia, caramelo, floral, frutal, nuez y verde. El análisis comparativo de las muestras se llevó a cabo mediante la prueba no paramétrica de Kruskal & Wallis. El grado de asociación de distintos pares de variables se examinó mediante un análisis correlacional. La relación entre muestras también se exploró mediante el análisis multivariado de componentes principales. Este análisis condujo a la identificación de las variables originales que más aportaron a la varianza de los dos primeros componentes principales. Diferencias estadísticamente significativas entre muestras se detectaron solo para el sabor a cacao. Las correlaciónes más altas se dieron entre las variables frutal y verde, frutal y astringencia, frutal y amargor, y frutal y nuez, la mayoría de signo negativo. Las variables con más aportación a la varianza (35.20%) del primer componente principal fueron frutal, verde y amargor. Acidez, floral y nuez hicieron la mayor aportación al segundo componente principal. La aparente estructuración de dos grupos muestrales en el plano definido sugiere semejanzas y diferencias en su perfil sensorial.
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This work analyzed the effect of infrared roasting at 100, 150, and 200°C on the main physical and chemical changes of cocoa. Raw and roasted cocoa were analyzed using Brunauer–Emmett–Teller, Fourier transform infrared spectroscopy, modulated differential scanning calorimetry (MDSC), thermogravimetric analysis (TGA), SPME, and GC‐MS. Using MDSC, the fusion of fat at around 35°C, and the desolvation of water and volatile compounds were identified. TGA detected loss of mass of various groups of chemical compounds, including those present pre‐roasting and generated during roasting. The unroasted cocoa's total sugar content of 2.71% decreased to 0.64% when roasted at 200°C, whereas roasting at 200°C generated seven (7) pyrazines. Tetramethylpyrazine is the most abundant, reaching the highest concentration when roasted at 150°C, but decreases when roasted at 200°C, due to the high temperature. To obtain the maximum production of favorable pyrazines, the temperature must be controlled based on the quality objectives of the final product. Practical applications The process of roasting cocoa is of great importance to the chocolate and derivatives industry. Knowledge of the chemical and physical changes that occur during roasting can help to optimize the operating conditions to obtain a better‐quality product, in particular by conserving and developing the flavor and aroma of fine Criollo cocoa varieties. This will support the industrialization of fine cocoas, presenting an option for improving the economic and social development of marginalized countries and communities.
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Roasting is an important process that contribute to formation of flavour compounds in cocoa beans. Pyrazines, a by-product of Maillard reaction is one of the character impact compounds that contribute to unique cocoa flavour. Unfortunately during roasting, carcinogenic acrylamide are also produced through Maillard reaction. Therefore, this study was focussed on optimising the roasting conditions using Central Composite Design (CCD) to produce superior quality cocoa beans with high concentration of pyrazines and low concentration of acrylamide. The roasting conditions used were temperatures in the range of 110°C to 160°C and time ranging from 15 min to 40 min. Roasting conditions significantly (p<0.005) affect the concentration of pyrazines in cocoa beans. However, the RSM analysis shows that the concentration of acrylamide in the beans was not influenced by the roasting conditions. Statistical optimisation based on maximum pyrazines and minimum acrylamide at temperature of 116°C and a time of 23 min produced the desirable value of 0.73. Hence, the optimized roasting conditions were able to produce high quality cocoa beans.
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This study concerns the influence of turning and fermentation method on quality of raw cocoa. Fermentation trials were conducted in wooden box, plastic box and in heaps with or not turning. Cocoa fermented in boxes during 4 days without stirring presented pH values above 5.0 while cocoa fermented in heaps presented pH 4.92. For fermentation with turnings, beans treated in wooden box were less acidic than beans fermented in plastic box, which recorded pH 4.75. Cocoa issued from all fermentations methods lasted 5 days without mixing presented pH above 5. Cocoa fermented in plastic box with turnings became acidic w ith pH 4.73 w hile acidity disappeared in beans fermented in heaps. A similar trend was observed in the titratable acidity of the dried beans. Cocoa fermented during 4 days w ithout turnings presented a high percentage of purple beans nearly 40% whatever the method. Percentages of defective, slaty and mouldy beans were below 4% with or without turnings. Cocoa beans fermented with turnings recorded about 10% of defectives beans whatever the process. Percentage of purple beans decreased to about 12% for cocoa fermented in wooden box. Naturally, percentage of brown beans increased for cocoa fermented both in wooden box and in heaps. All the beans showed no sign insect damages, and negligible levels of internal molding whatever the turning and the methods of fermentation.
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The cocoa beans of the Ivory Coast variety were convectively and microwave roasted. The effects of roasting conditions on the principal physicochemical attributes (water and fat contents, total and volatile acidity) of roasted cocoa beans and the properties of fat extracted from this material (acidity, saponification index, iodine index, peroxide value, light refraction coefficient, polar fraction content, and Fatty Acid profile, absorbancy of 1 and 10% solution in hexane) were examined. The characteristics of roasted and raw cocoa beans and their lipid fractions were compared. Results of analyses showed that convective roasting for 35 min at 135°C, air flow rate 1.0mxs-1 and relative humidity RH of 0.45% caused the least advanced changes in fat quality while microwave roasting promoted oxidation of lipids although the quality of roasted cocoa beans was the best. Granos de cacao de la variedad Costa de Marfil se han sometido a tostado mediante convección y microondas. Se ha estudiado el efecto de las condiciones de tostado sobre los atributos físico-químicos principales (contenido de agua y grasa, acidez total y volátil) del cacao en grano tostado y las propiedades de la grasa extraída de este material (Acidez, índice de saponificación, índice de peróxidos, índice de yodo, índice de refracción, contenido de fracción polar, perfil de ácidos grasos, absorbancia de una solución al 10% en hexano). Se han comparado las características de los granos de cacao tostados y crudos y sus fracciones lipídicas. Los resultados de los análisis mostraron que el tostado mediante convección durante 35 minutos a 135°C, con un caudal de aire de 1,0 m s-1 y HR de 0,45 causó los menores cambios en la calidad de grasa mientras que el tostado mediante microondas promovió en mayor medida la oxidación de los lípidos aunque la calidad de los granos de cacao tostado fue mejor.
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Chocolate and cocoa are extensively used in many cultures. Although their composition has been studied, the functional significance of the components has not been as well defined. There are indications that cocoa constituents exert beneficial effects on human health, and therefore cocoa and chocolate may be considered functional foods. The use of functional foods to modulate human health has gained greater significance in recent years, and chocolate is widely consumed throughout society. We performed an extensive review of literature in both animal and human systems with respect to composition, bioavailability, comparative analysis with other food products and, especially, implications for cardiovascular disease and the human immune system. Although chocolate contains a high amount of saturated fats, the two major fatty acids are palmitic and stearic acid, which appear to have fewer implications for progression of coronary artery disease than other saturated fatty acids. In addition, the implications of flavonoids and other polyphenols in chocolate as antioxidants are significant, and their ability to modulate the immune system may also be applicable to infection and neoplasia. In this review, we attempt to place these issues in perspective and to provide the reader with an extensive summary of the literature on chocolate and cocoa and their potential mechanisms of action with respect to human health.
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Thirty-two samples of commercially available Greek wines were analysed in order to determine the content of biogenic amines. The method involves pre-column dansylation of the amines and subsequent solid phase extraction (SPE) of the derivatives through C 18 car-tridges. For the analysis, RP-HPLC (reversed phase-high performance liquid chromatography) coupled with fluorimetric detection at excitation and emission wavelengths of 320 and 523 nm, respectively was used. All amines measured had recoveries over 85%. The high-est detection limit was for agmatine (0.18 mg l À1). Putrescine, cadaverine, histamine and isoamylamine are the most abundant amines in the samples analysed. The relative concentrations of biogenic amines expressed in mg l À1 had as follows: putrescine > histamine > iso-amylamine > ethylamine > methylamine > cadaverine = tyramine = agmatine = tryptamine. Higher amounts of biogenic amines were generally detected in wines, aged for long periods in barrels or in bottles. However, young wines contained lower amounts of these com-pounds as they were directly bottled after winemaking and have not undergone any further maturation processing. Moreover, less acid wines gave rise to higher histamine contents.
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Raw cocoa is the processed and traded form of the cocoa seed. Fresh seeds undergo fermentation and a drying process before they are prepared for transport and shipping. Depending on the local situation in the producer region the seeds are collected from big estates and are fermented and dried in big lots or they originate from small farmer's crop trees. In the subsequent transport and trading chain raw cocoas may be mixed and stored before they finally are sold and brought to the consumer countries. Local or regional variations in cocoa plant material, fermentation procedures and drying processes finally result in a typical traded good with respect to the amino acids, which form an important part of the flavour precursors. These free amino acids and their composition result from the fermentation procedure of fresh seeds. In the course of the fermentation specific cleavage of cocoa storage proteins delivers the amino acid patterns. In this study the variation of free amino acid amount and distribution of 108 commercially fermented and traded cocoa samples and two Theobroma grandiflorum (Willd. ex Spreng.) K. Schum samples were determined. This examination showed clearly, that content and distribution of free amino acids in raw cocoa from different origins vary greatly (5–25mgg−1 fatfree dry matter), in some cases country and even region-specific differences were apparent. It is important to notice typical, region-specific variations in the amounts and compositions of free amino acids.
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Almost 500 clones of wild cocoa trees (Theobroma cacao L.) grown from pods collected in 1987 from wild mother-trees in the Camopi and Tanpok river basins (southeastern French Guiana) have been distributed in around fifteen cocoa producing countries since 1988. The name of those clones always bears the GU prefix (for “Guyane”, i.e. French Guiana). All the germplasm of the same geographical origin present in the CIRAD collection at Paracou-Combi (Sinnamary, French Guiana), i.e. more than 1600 trees, has been abundantly studied for its morphological characterization, its agronomic assessment or its genetic diversity. Other assessment work, primarily on resistance to certain diseases, has been carried out by CIRAD in Montpellier, or in various countries by other organizations.In order to simplify the choice for breeders faced with a large number of GU clones and wishing to use some of them, an overview is presented here of the results obtained with this germplasm for various selection criteria such as productivity, the yield:vigour ratio (cropping efficiency), pod filling, bean size, resistance to pests and diseases, compatibility, sensory qualities, etc. The results obtained for resistance of this material to witches’ broom disease and black pod rot show a globally high level of resistance, making the GU germplasm a new and major potential source of resistance to those diseases. The same seems to apply for resistance to mirid damage. The yield levels achieved in French Guiana, along with cropping efficiency, are noteworthy in some families. The first results acquired reveal a substantial heterosis effect when GU clones are hybridized with other groups.Given their distribution in several countries, the known individual qualities and performance of some GU clones present at the Reading quarantine station (UK) are indicated. A selection of clones that are of interest or promising for incorporation in breeding programmes is provided for each criterion.
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Dopamine is an endogenous catecholamine that modulates many functions including behavior, movement, nerve conduction, hormone synthesis and release, blood pressure, and ion fluxes. Dopamine receptors in the brain have been classically divided into D1 and D2 subtypes, based on pharmacological data. However, molecular biology techniques have identified many more dopamine receptor subtypes. Several of the receptors cloned from the brain correspond to the classically described D1 and D2 receptors. Several D1 receptor subtypes have been cloned (D1A, D1B, and D5) and are each coupled to the stimulation of adenylyl cyclase. The D2 receptor has two isoforms, a shorter form, composed of 415 amino acids, is termed the D2short receptor. The long form, called the D2long receptor, is composed of 444 amino acids; both are coupled to the inhibition of adenylyl cyclase. The D3 and D4 receptors are closely related to, but clearly distinct from, the D2 receptor. They have not yet been linked to adenylyl cyclase activity. Outside of the central nervous system, the peripheral dopamine receptors have been classified into the DA1 and DA2 subtypes, on the basis of synaptic localization. The pharmacological properties of DA1 receptors roughly approximate those of D1 and D5 receptors, whereas those of DA2 receptors approximate those of D2 receptors. A renal dopamine receptor with some pharmacological features of the D2 receptor but not linked to adenylyl cyclase has been described in the renal cortex and inner medulla. In the inner medulla, this D2-like receptor, termed DA2k, is linked to stimulation of prostaglandin E2 production, apparently due to stimulation of phospholipase A2. Of the cloned dopamine receptors, only the mRNA of the D3 receptor has been reported in the kidney. The DA1 receptor in the kidney is associated with renal vasodilation and an increase in electrolyte excretion. The DA1-related vasodilation and inhibition of electrolyte transport is mediated by cAMP. The role of renal DA2 receptors remains to be clarified. Although DA1 and DA2 receptors may act in concert to decrease transport in the renal proximal convoluted tubule, the overall function of DA2 receptors may be actually the opposite of those noted for DA1 receptors. Dopamine has been postulated to act as an intrarenal natriuretic hormone. Moreover, an aberrant renal dopaminergic system may play a role in the pathogenesis of some forms of hypertension. A decreased renal production of dopamine and/or a defective transduction of the dopamine signal is/are present in some animal models of experimental hypertension as well as in some forms of human essential hypertension.
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Studies were conducted to evaluate effects of pod storage (as a means of pulp pre-conditioning) and fermentation time on the fermentative quality and appearance of Ghanaian cocoa beans. The fermentative quality (cut test and fermentation index [FI]) and colour (L, a, b) of the cocoa beans were studied using standard methods. Increasing pod storage and fermentation time significantly (P<0.05) influenced the fermentative quality and appearance of the beans. Fermentation caused significant increases in FI at all periods of pod storage whilst increasing pod storage resulted in darker, yellower and less red beans. Cut test scores revealed that storage of pods for 7 and 14 days increased the percentage of brown beans by 15 and 38% respectively by the sixth day of fermentation. Thus, Ghanaian cocoa pods could be stored for up to 14 days prior to fermentation with optimum fermentative quality and desired colour attained after 4 days of fermentation.
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The decarboxylation of phenylalanine in the presence of methyl 13-hydroperoxyoctadeca-9,11-dienoate (LOOH), 2,4-decadienal (DD), 4,5-epoxy-2-decenal (ED), 4-hydroxy-2-nonenal (HN), and 4-oxo-2-nonenal (ON) was studied both to explore the potential of lipid oxidation products (LOP) to produce amino acid decarboxylation and to understand the reaction pathways responsible for this degradation. All assayed LOP were able to decarboxylate phenylalanine, but their reactivity decreased in the following order when the reaction was carried out under non-oxidative conditions: DD > ED ≈ LOOH > HN ≈ ON. The reaction pathway is proposed to take place by decarboxylation of the imine formed between the amino group of the amino acid and the carbonylic group of the oxidized lipid. This decarboxylation is facilitated due to the formation of a relatively stable azomethine ylide after the loss of carbon dioxide from a 5-oxazolidinone intermediate. The azomethine ylide would, finally, evolve into new conjugated imines, which are the origin of both β-phenylethylamine and phenylacetaldehyde, which was also detected in the reaction mixtures. The activation energy (Ea) for the phenylalanine decarboxylation in the presence of 2,4-decadienal was 54 kJ/mol. Although additional studies are needed to determine the contribution of the chemical pathways described in this study to the overall biogenic amine formation in foods, this study provides the chemical basis both to understand how biogenic amines can be produced chemically from amino acids in the presence of lipid-derived carbonyls and to propose potential inhibitors in this route.
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The types and levels of free bioactive amines in different corn products were determined. The amines were analyzed by ion pair-HPLC, post-column derivatization with o-phthalaldehyde and fluorimetric detection. Fresh sweet corn contained mainly spermidine followed by putrescine. Spermine, cadaverine, phenylethylamine, histamine and agmatine were also present at low levels. The profile and levels of amines changed significantly in canned and dried corn. Putrescine was the prevalent amine in canned corn whereas spermine was prevalent in dried corn. Germinated corn had significantly higher spermidine, spermine and putrescine levels. The embryo of the corn contained significantly higher spermine levels compared to the endosperm. These results indicate that corn is a good source of polyamines and that the different types of corn products available can be used to provide a profile of amines according to specific dietary need.
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Summary 2-Phenylethylamine was extracted from cocoa nibs and chocolates and analysed by coupled gas chromatography-mass spectroscopy. The amine concentration increases in fermentation of cocoa and decreased during roasting and alkalization. Its concentration in chocolates is dependent on non-fat cocoa contents. Previously unreported aldimines were found in cocoa powders, which arise from the condensation of phenylethylamine and aldehydes. The main component of these products isN-phenylmethyl-N-phenylmethylene amine (CAS 3240-95-7).
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The levels of ten free bioactive amines, as well as pH and color characteristics, were determined in different types and brands of instant coffee. The amines were extracted with trichloroacetic acid and quantified by ion-pair HPLC, post-column derivatization with o-phthalaldehyde and fluorimetric detection. Overall, nine amines were detected: serotonin, cadaverine, tyramine, spermidine, putrescine, histamine, agmatine, phenyletylamine and spermine. Tryptamine was not detected in any sample. Tyramine was present in every sample, followed by cadaverine and serotonin. Total amine levels in the dry instant coffee varied from 0.28 to 2.76mg/100g. Overall, serotonin was present at higher levels followed by cadaverine, tyramine and spermidine. Significantly higher tyramine levels were found in decaffeinated coffee and higher cadaverine levels were detected in decaffeinated and organic coffee. The levels of amines varied among lots of the same brand and among brands. The color characteristics varied among types of instant coffee. The pH of the beverage varied from 4.86 to 5.15, with higher levels in decaffeinated coffee. There was significant positive correlation between pH and the levels of tyramine and agmatine. Investigations are needed to ascertain the impact of these amines on coffee flavor and on human health, and to determine the factors which affect amine formation and accumulation in instant coffee.
Article
Tetrahydro-beta -carbolines (TH beta Cs), potential neuroactive alkaloids, were found in chocolate and. cocoa. 6-Hydroxy-1-methyl-1,2,3,4-tetrahydro-beta -carboline (60HMTH betaC), 1,2,3,4-tetrahydro-beta -carboline-3-carboxylic acid (THCA), 1-methyl-1,2,3,4-tetrahydro-beta -carboline-3-carboxylic acid (MTCA) in both diastereoisomers (1S,3S and 1R,3S), and 1-methyl-1,2,3,4-tetrahydro-beta -carboline (MTH betaC), besides serotonin and tryptamine biogenic amines, were identified and quantified in dark chocolate, milk chocolate, cocoa, and chocolate-containing cereals by RP-HPLC-fluorescence and HPLC-MS. For each TH betaC, the concentration ranges were determined: 60HMTH betaC (0.16-3.92 mug/g), THCA (0.01-0.85 mug/g), 1S,3S-MTCA (0.35-2 mug/g), 1R,3S-MTCA (0.14-0.88 mug/g), and MTH betaC (nd-0.21 mug/g). The highest content was generally found in chocolates and cocoas, but cereals containing chocolate also showed an appreciable amount of TH beta Cs. The possible biological implications of this novel group of alkaloids in chocolate are discussed.
Article
A selective and sensitive ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-MS) method was developed for the simultaneous determination of ten biogenic amines (tryptamine, 2-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine, adrenaline, dopamine and spermine) in a thymopolypeptides injection from the Chinese market for the first time. Biogenic amines (BAs) were pre-column derivatised by dansyl chloride after direct sample dilution. Dansylated amines were separated on an ACQUITY UPLC BEH Shield RP18 column (2.1mm×150mm I.D., 1.7μm) using a gradient elution. Quantification was done by monitoring fragment ions of each derivative under the MS mode of multiple reaction monitoring (MRM). A satisfactory result of method validation was obtained. The linearity ranged from 0.32 to 1182.9μg/L and the correlation coefficients (r) for all amines were above 0.99. The LOD ranged from 0.08μg/L for 2-phenylethylamine and tyramine to 8.00μg/L for adrenaline; the LOQ ranged from 0.32μg/L for 2-phenylethylamine to 12.12μg/L for dopamine. The recovery ranged from 75.8 to 110.3% after spiking standard solutions of BAs to a sample at three levels. The intra and inter-day precision RSD were 0.78-8.85% and 1.39-9.93% respectively. Eighty-four injections were analyzed by this method. Nine biogenic amines were found in them except adrenaline. Moreover, the relationship between the result of test for depressor substances and the content of BAs was statistically analyzed.
Article
Twenty-one Natto products currently distributed in Korea were analysed for biogenic amine contents and tested to determine physicochemical and bacterial contributions to biogenic amine formation. Among them, nine products (about 43%) had β-phenylethylamine or tyramine contents greater than the toxic dose (30mg/kg and 100mg/kg, respectively) of each amine, although no products showed total amounts of biogenic amines above the harmful level (1000mg/kg), which indicates that the amounts of biogenic amines in some Natto products are not within the safe level for human health. From four different Natto products, that contained noticeable levels of β-phenylethylamine and tyramine, 80 bacterial strains were isolated. All the strains were identified to be Bacillus subtilis and highly capable of producing β-phenylethylamine and tyramine. Therefore, it seems likely that the remarkable contents of β-phenylethylamine and tyramine in Natto predominantly resulted from the strains highly capable of producing those amines present in the food.
Article
The effect of roasting on the levels of amines in high and low quality coffee was investigated. Arabica green coffee samples previously classified by cup as soft (high quality) and rio (low quality) were roasted at 220 °C. Bean samples were collected every 4 min during roasting. HPLC analysis was carried out for detection and quantification of bioactive amines. Putrescine was the prevailing amine in both samples, followed by spermidine and spermine. Putrescine levels were significantly higher for the rio sample compared to the soft one. Also, both histamine and tryptamine were only present in the rio sample. There was a significant decrease in total amine content during roasting, with degradation of putrescine, spermine, histamine and tyramine taking place mostly during the drying stage. Degradation of spermidine occurred at a slower rate.
Article
a b s t r a c t The contents of protein and non-protein (free and protein-bound) tryptophan and of proteins in cocoa beans of various origin were determined. Protein concentrations varied from 11.8 g/100 g in beans from the Dominican Republic to 15.7 g/100 g in roasted beans from the Ivory Coast. The highest protein tryp-tophan content was found in cocoa beans from Ecuador. Madagascar beans had the highest value of free tryptophan and Echeandia the lowest (17.26 and 6.39 mg/100 g, respectively). Tryptophan was bound to water-soluble proteins as well as to proteins soluble in buffer solution (pH 8.9) and in 70% ethanol. In particular, Dominican Republic cocoa contained the highest amount of tryptophan bound to water-solu-ble proteins. Very little tryptophan was linked to proteins soluble in alkaline or ethanol solutions, and values ranged from 0.96 to 3.04 and from 0.24 to 1.21 mg/100 g of dry defatted cocoa sample, respectively.
Article
In this study, commercial Malaysian cocoa beans (SMC1A) were roasted in a forced airflow-drying oven for 20, 30, 40 and 50 min at 120, 130, 140, 150, 160 and 170C. The products were evaluated for flavor compounds and sensory evaluation (as dark chocolate). The volatile fraction was isolated using the combined steam distillation–extraction procedure and was identified by gas chromatography–mass spectrometry. A quantitative descriptive analysis was used to evaluate the flavor intensity of the chocolates using a 9-point rating scale for selected flavor attributes, namely astringency, bitter taste, sour taste, cocoa and burnt. Panelists were asked to smell and taste the sample against a standard chocolate. It was found that there were significant differences in flavor compounds between the different conditions of roasting. The main flavoring compounds identified composed of aliphatic and alicyclic groups such as alcohol and ester, and heterocyclic groups such as pyrazine and aldehyde. A total of 19 volatile major components were identified: nine pyrazines (2,5-dimethyl-, 2,3-dimethyl-, 2-ethyl-6-methyl-, trimethyl-, 3-ethyl-2,5-dimethyl-, tetramethyl-, 2-ethenyl-6-methyl- and 3,5-dimethyl-2-methylpyrazine); five aldehydes (5-methyl-2-phenyl-2-hexenal, benzaldehyde, benzalacetaldehyde and α-ethyliden-benzenacetaldehyde); one methyl ketone (2-nonanone); two alcohols (linalool and 2-heptanol); and two esters (4-ethylphenyl acetate and 2-phenylethyl acetate). Based on the flavor profile of the compounds identified, an optimum production of the major flavoring compounds such as pyrazine, aldehyde, ketone, alcohol and ester occurred at 160C for 30 min of roasting. Trimethylpyrazine and tetramethylpyrazine compounds together with 5-methyl-2-phenyl-2-hexanal were found to be good indicators for the evaluation of the roasting process. However, based on chocolate evaluation, the best roasting temperature was 150C for 30 min, which gave the lowest astringency and at the same time gave the lowest bitter taste and low level of sour and burnt tastes. At 150C roasting temperature, the desirable cocoa flavor was at its optimum. Correlation coefficients among certain volatile flavor and sensory characteristics of cocoa beans and dark chocolate were significant (P < 0.05).
Chapter
The effectiveness of different compounds in the generation of acrylamide (AA) from asparagine, was determined by reacting asparagine with mono-, diand polysaccharides, as well as four different oxo-compounds known to be involved in carbohydrate metabolism/degradation. Quantitation of AA formed either under aqueous conditions or in low water model systems revealed glucose and 2-oxopropionic acid as the most effective compounds in AA generation, when reacted in model systems with a low water content (about 1 mol-% yield). Interestingly, heating of asparagine in the presence of 2-oxopropionic acid generated quite high amounts of 3-aminopropionamide (3-APA), which itself effectively generated AA upon heating in aqueous solution, as well as in low water systems. Because this is the first report on amounts of 3-APA generated by Maillard-type reactions, the general role of 3-APA as key intermediate in AA formation is discussed in detail. In addition, first results on the development and application of an HPLC/fluorescence method for AA quantitation are presented.
Chapter
The effects of theobromine in man are underresearched, possibly owing to the assumption that it is behaviourally inert. Toxicology research in animals may appear to provide alarming results, but these cannot be extrapolated to humans for a number of reasons. Domestic animals and animals used for racing competitions need to be guarded from chocolate and cocoa-containing foods, including foods containing cocoa husks. Research ought to include caffeine as a comparative agent, and underlying mechanisms need to be further explored. Of all constituents proposed to play a role in our liking for chocolate, caffeine is the most convincing, though a role for theobromine cannot be ruled out. Most other substances are unlikely to exude a psychopharmacological effect owing to extremely low concentrations or the inability to reach the blood–brain barrier, whilst chocolate craving and addiction need to be explained by means of a culturally determined ambivalence towards chocolate. KeywordsChocolate-Cocoa-Comparative-Craving-Liking-Myths-Pharmacology-Psychology-Theobromine-Toxicology
Article
The levels of free and total tryptophan and of 5-hydroxytryptophan (5-HTP) were investigated in green and roasted grains and beverages of Coffea arabica L. (Arabica) and Coffea canephora Pierre var. robusta (Robusta). Grains were light, medium and dark roasted. Free and protein tryptophan were extracted before and after hydrolysis. The levels of tryptophan and 5-HTP were quantified simultaneously by ion-pair HPLC and fluorimetric detection after derivatisation with o-phthalaldehyde. Robusta green coffee had higher total and protein tryptophan, whereas Arabica had higher free tryptophan levels. 5-HTP was not detected in the samples before and after roasting. Free tryptophan was completely degraded during roasting. Roasting significantly affected protein tryptophan. The rate of loss was smaller in Arabica compared to Robusta at every roasting degree. A beverage prepared the Brazilian way with a medium-roasted coffee provided 1.4–2.5 mg tryptophan/50 ml cup.
Article
The profile and levels of bioactive amines in green and roasted coffee were investigated. Coffea arabica L., variety ‘catuaı́ vermelho’, was harvested in São Sebastião do Paraı́so, state of Minas Gerais, Brazil. The green coffee was roasted at two degrees—American and French (300 °C for 6 and 12 min, respectively). The samples were analysed for bioactive amines. Roasted samples were also analysed for moisture content, water activity and L∗a∗b∗ colour characteristics. Total amine levels in green coffee ranged from 3.03 to 4.44 mg/100 g. The predominant amines in green coffee were serotonin and putrescine, followed by spermidine and spermine. The degree of roasting did not affect moisture content or water activity of the coffee bean. Hue angle and saturation were higher for American than for French coffee. The profile and levels of bioactive amines in roasted coffee differed significantly from green coffee. The prevailing amine in roasted coffee was serotonin, followed by spermidine. Putrescine and spermine were not detected in roasted coffee. The presence of agmatine was detected in French roasted coffee. American roasted coffee had lower amine levels than French, which indicated that, the stronger the degree of roasting, the higher were the total levels of amines.
Article
A rapid ultra-performance liquid chromatographic (UPLC) method for the determination of biogenic amines (putrescine, cadaverine, spermidine, spermine, phenylethylamine, histamine, tyramine and tryptamine) in selected food samples is described. The eight biogenic amines, which are the most important to be determined in food samples, were derivatized with dansyl chloride prior to UPLC separation. The dansylated amines were separated on an Agilent Zorbax Eclipse XDB – C18 column (50 × 4.6 mm ID, 1.8 μm) using gradient elution with a binary system of acetonitrile–water, a flow rate of 1.0 ml/min and UV detection at 225 nm. The analysis is very fast, all amines are well resolved and are eluted from the column in less than 6 min. The average repeatability of the method ranged between 1.02% and 2.14%. Limits of detection (LODs) for considered amines ranged between 0.032 and 0.098 μg/l; calibration curves showed very good linearity (r = 0.9994–1.0000). The method was applied to the analysis of amines in pork, beef, chicken and fish meat, cheese and edible mushrooms.
Article
Recent trends in food marketing suggest that cocoa products, besides being favourite sweets among consumers, also present multiple-benefit foodstuffs, which are becoming objects of increased scientific research, mainly because of their interesting phytochemical composition. UV/VIS spectrophotometric and high-performance liquid chromatography (HPLC-PDA) methods were applied in order to compare the composition of polyphenols and methylxanthines in commercial cocoa products affected by different extraction solvents. Antioxidant capacity of water and methanol extracts was evaluated using DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) and FRAP (ferric reducing/antioxidant power) assays. The obtained results confirmed that the content of polyphenols and methylxanthines, as well as the antioxidant capacity of cocoa products depend on the content of their cocoa solids. Among the tested cocoa products, the highest content of bioactive compounds (polyphenols and methylxanthines) was determined in extracts of cocoa products with the highest content of cocoa solids (cocoa liquor, cocoa powder and dark chocolate with 88% cocoa solids), while the lowest content was determined in milk chocolate and cocoa bar extracts. The most abundant phenolic compound in cocoa extracts was (−)-epicatechin, while the most abundant methylxanthine was theobromine. In comparison with water, 70% methanol demonstrated higher efficiency for the extraction of the studied bioactive compounds from cocoa products.